Unsaturated compounds containing carbamate terminal groups or urea terminal groups

ABSTRACT

The invention relates to a compound containing at least one unsaturated, radically or cationically polymerizable group and at least one carbamate terminal group or urea terminal group.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to unsaturated compounds containing carbamate orurea end groups and to their use in dual cure systems.

2. Description of the Background

The feature of dual cure systems is that they are curable by means oftwo independent curing mechanisms, e.g., radiation curing, moisturecuring, oxygenated curing or thermal curing. There is a particulardesire for systems which following the application of the coatingcomposition may be precured by very short exposure to UV light to give aflexible film which is dust-dry. This film should then either bethermally postcurable or should continue to cure just on storage in airover the course of a few days until a hard film has formed which has thefinal desired service properties. This type of two-stage curing is ofparticular importance since it allows the processors of the coatingsystems to coat an article with a film in a first workstep and in asecond step to process said film further, in particular to give theready-coated and irradiated article a certain profile using pressure. Atthe time of their deformation in the second workstep, therefore, thefilms or sheets must have already undergone initial curing, so that theydo not stick to the tools in the course of deformation; on the otherhand, however, they must not already be so hard that they tear whenstretched and deformed.

The phrase “dual cure” refers in accordance with the invention to acuring process which takes place by way of at least two mechanisms,namely radiation, moisture, oxidative and/or thermal curing.

Dual cure coatings which are photochemically polymerizable and possess asecondary curing mechanism, by way of alkoxysilane groups, for example,are known from U.S. Pat. No. 5,523,443; such structures may also containcarbamate linkages. Said document describes polymerizable systems whichcan be cured both by ultraviolet exposure and by way of a furthermechanism. These systems consist of analkoxysilyl-urethane(meth)acrylate and a (meth)acrylate or vinyl etheras reactive diluent.

Moreover, U.S. Pat. No. 5,075,384 discloses unsaturated carbamatesobtained by reacting unsaturated isocyanates with the hydroxyl groups ofstyrene-allyl alcohol copolymers. The carbamate groups that have formedserve merely as linkers for the introduction of unsaturated groups. Thesystems described therein are curable by UV and dry oxidatively.

Further documents, examples being U.S. Pat. Nos. 4,138,299, 4,173,682,4,415,604, and EP-A 549 116, describe resins which can be cured by meansof radiation and atmospheric moisture. Both the oxidative drying and theair curing, however, are very slow processes which proceed in anuncontrolled fashion.

U.S. Pat. No. 4,138,299 describes a radiation- and moisture-curablecoating system composed of 15-60% by weight of acrylate as reactivediluent and 40-85% by weight of an isocyanate-terminated prepolymerformed by reacting polyesterdiols and -triols with aliphaticdiisocyanates, 5-15% of the available isocyanate groups being reactedwith hydroxy acrylates.

U.S. Pat. No. 4,173,682 describes a method of coating a substrate with aradiation- and moisture-curable coating comprising anisocyanato-containing adduct of a (meth)acrylic acid hydroxy ester and apolyisocyanate, a polyfunctional hydroxy compound, and a photoinitiator.The components may not be combined until shortly before application inorder to prevent unwanted hardening.

U.S. Pat. No. 4,415,604 describes a UV- and moisture-curable coatingcomposition comprising a polyetherdiol or -triol containing isocyanateend groups, a (meth)acrylate as reactive diluent, and a polymerizationinitiator.

EP-A 549 116 describes a dual cure composition which comprises reactivediluents and an isocyanate adduct that carries free isocyanate groupsand free, photopolymerizable, ethylenically unsaturated groups.

Unsaturated isocyanato acrylates of this kind which contain not only thephotochemically curable acrylate groups but also free isocyanates are,however, not stable on storage or else must be stored in the absence ofmoisture, which is awkward.

EP-A 844 286 describes a powder coating system for powder coatingmaterials that comprises not only a UV free-radical initiator but alsoan initiator which can be activated thermally. This text remarks thatliquid systems based on thermal peroxide initiators only have relativelyshort storage lives.

Moreover, systems which cure by means of heat alone and which crosslinkby way of carbamates or ureas are known—from U.S. Pat. No. 5,770,650 forexample. U.S. Pat. No. 5,770,650 describes a curable compositioncontaining carbamate or urea and ester or amide groups and a curingreagent. The possibility of a UV cure is not contemplated.

Also known are unsaturated isocyanato acrylates which in addition to thephotochemically curable acrylate groups also contain free isocyanates.However, such binders lack storage stability.

More stable on storage are the radiation-curable and thermally curablebinders known from DE-A 26 31 949, containing blocked polyisocyanates.DE-A 26 31 949 describes radiation-curable binders which comprise ablocked polyisocyanate, in the form of oxime, malonate, acetoacetate,caprolactone, phenol, etc. The coating films that have formed receive athermal aftertreatment. The manner of thermal crosslinking describedtherein, which involves the reelimination of isocyanates, is not alwaysunproblematic, however, with regard to the elimination products thatform (e.g., pyrazoles, triazoles), some of which remain in the film andact, for example, as plasticizers. Consequently, there continues to be aneed for alternative crosslinking mechanisms.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide dual cure systemsfor radiative and thermal curing which are stable on storage and whichin condensation reactions release only volatile elimination products.

We have found that this object is achieved with compounds containing atleast one unsaturated free-radically or cationically polymerizable groupand at least one carbamate and/or urea end group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The number-average molecular weight, M_(n), of these compounds,determined by gel permeation chromatography using tetrahydrofuran aseluent and polystyrene as standard, may amount, for example, to between200 and 200 000, preferably between 250 and 100 000, with particularpreference between 350 and 50 000, and in particular between 500 and 30000 g/mol.

The amount of unsaturated free-radically or cationically polymerizablegroups per 100 g of compound may, for example, amount to at least 0.01mol, perferably at least 0.05 mol, with particular preference at least0.1 mol, and in particular at least 0.2 mol.

The amount of carbamate and/or urea end groups per 100 g of compound mayamount, for example, to at least 0.01 mol, preferably at least 0.05 mol,with particular preference at least 0.1 mol, and in particular at least0.2 mol.

The free-radically or cationically polymerizable groups and thecarbamate and/or urea end groups may be connected to one anotherarbitrarily; they may be attached, for example, to addition polymers,polycondensates or polyadducts.

These may, for example, be polymers or copolymers of monomers that areknown per se, polyesters, polyamides, polyimides, polyurethanes,polyureas, polyepoxides or polyethers.

Monomers from which polymers or copolymers may be constructed include,for example, esters of (meth)acrylic acid with alcohols of from 1 to 20carbon atoms, e.g., methyl(meth)acrylate, ethyl (meth)acrylate,butyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, vinylaromaticcompounds, e.g., styrene, divinylbenzene, α,β-unsaturated nitriles,e.g., acrylonitrile, methacrylonitrile, vinyl esters, e.g., vinylacetate, vinyl propionate, halogenated ethylenically unsaturatedcompounds, e.g., vinyl chloride, vinylidene chloride, conjugatedunsaturated compounds, e.g., butadiene, isoprene, chloroprene,monounsaturated compounds, e.g., ethylene, propylene, 1-butene,2-butene, iso-butene, cyclic monounsaturated compounds, e.g.,cyclopentene, cyclohexene, cyclododecene, n-vinylformamiade, allylaceticacid, vinylacetic acid, monoethylenically unsaturated carboxylic acidsof from 3 to 8 carbon atoms and their water-soluble alkali metal salts,alkaline earth metals salts or ammonium salts, examples being acrylicacid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleicacid, citraconic acid, methylenemalonic acid, crotonic acid, fumaricacid, mesaconic acid, and itaconic acid, maleic acid,N-vinylpyrrolidone, N-vinyllactams, such as N-vinylcaprolactam,N-vinyl-N-alkylcarboxamide or N-vinylcarboxamides, such asN-vinylacetamide, N-vinyl-N-methylformamide andN-vinyl-N-methylacetamide, vinyl ethers, e.g., methyl vinyl ether, ethylvinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinylether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinylether, 4-hydroxy butyl vinyl ether, and mixtures thereof.

Preference is given to the free-radically or cationically polymerizablegroups and the carbamate or urea end groups being attached topolyurethanes.

The polyurethanes (A) of the invention comprise as constituentcomponents substantially:

-   -   a) at least one organic aliphatic, aromatic or cycloaliphatic        di- or polyisocyanate,    -   b) at least one compound containing at least one        isocyanate-reactive group and at least one free-radically        polymerizable unsaturated group and/or a cationically        polymerizable group,    -   c) at least one compound containing at least one        isocyanate-reactive group and a carbamate or urea end group,    -   d) if desired, at least one compound containing at least one        isocyanate-reactive group and at least one dispersing group,    -   e) if desired, at least one compound containing at least two        isocyanate-reactive groups, and    -   f) if desired, compounds other than a) to d) containing at least        one isocyanate-reactive group.

Further polyurethanes of the invention additionally comprise ascomponent (B) at least one compound containing at least one group thatcan crosslink with the carbamate groups. We have found that the objectmentioned earlier is likewise achieved by aqueously processiblepolyurethane dispersions essentially comprising

-   -   (A) a polyurethane wherein component d) is present and    -   (B) at least one compound containing at least one group that can        crosslink with the carbamate groups,    -   (C) if desired, one or more initiators which can be activated        photochemically and/or thermally, and    -   (D) if desired, further typical coatings additives.

The compounds (B), (C), and (D) may also be added to the polyurethanesif the desire is to provide coating formulations for preparing dual curecoating materials.

Examples of suitable components a) include aliphatic, aromatic andcycloaliphatic di- and polyisocyanates having an NCO functionality of atleast 1.8, preferably from 1.8 to 5, and with particular preference from2 to 4, and also their isocyanates, biruets, allophanates, anduretdiones.

The diisocyanates preferably comprise isocyanates of from 4 to 20 carbonatoms. Examples of customary diisocyanates are aliphatic diisocyanatessuch as tetramethylene diisocyanate, hexamethylenediisocyanate(1,6-diisocyanatohexane), octamethylene diisocyanate,decamethylene diisocyanate, dodecamethylene diisocyanate,tetradecamethylene diisocyanate, lysine diisocyanate derivatives,tetramethylxylylene diisocyanate, trimethylhexane diisocyanate ortetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4′- or2,4′-di(isocyanatocyclohexyl)methane,1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophoronediisocyanate), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or 2,4- or2,6-diisocyanato-1-methylcyclohexane, and also aromatic diisocyanatessuch as 2,4- or 2,6-tolylene diisocyanate and isomer mixtures thereof,m- or p-xylylene diisocyanate, 2,4′- or 4,4′-diisocyanatodiphenylmethaneand isomer mixtures thereof, 1,3- or 1,4-phenylene diisocyanate,1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate,diphenylene 4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethylbiphenyl,3-methyldiphenylmethane 4,4′-diisocyanate, tetramethylxylylenediisocyanate, 1,4-diisocyanato benzene or diphenyl ether4,4′-diisocyanate.

Mixtures of said diisocyanates may also be present.

Preference is given to hexamethylene diisocyanate,1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, anddi(isocyanatocyclohexyl)methane.

Suitable polyisocyanates include polyisocyanates containing isocyanurategroups, uretdione diisocyanates, polyisocyanates containing biuretgroups, polyisocyanates containing urethane or allophanate groups,polyisocyanates containing oxadiazinetrione groups, uretonimine-modifiedpolyisocyanates of linear or branched C₄-C₂₀-alkylene diisocyanates,cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms oraromatic diisocyanates having a total of 8 to 20 carbon atoms, ormixtures thereof.

The di- and polyisocyanates which can be used preferably have anisocyanate group content (calculated as NCO, molecular weight=42) offrom 10 to 60% by weight, based on the di- and polyisocyanate (mixture),more preferably from 15 to 60% by weight, and with particular preferencefrom 20 to 55% by weight.

Preference is given to aliphatic and/or cycloaliphatic di- andpolyisocyanates, examples being the aliphatic and cycloaliphaticdiisocyanates mentioned above, or mixtures thereof.

Preference is further given to

-   -   1) Polyisocyanates of aromatic, aliphatic and/or cycloaliphatic        diisocyanates, containing isocyanurate groups. Particular        preference is given here to the corresponding aliphatic and/or        cycloaliphatic isocyanato isocyanurates and particularly to        those based on hexamethylene diisocyanate and isophorone        diisocyanate. The present isocyanurates particularly comprise        trisisocyanatoalkyl and trisisocyanatocycloalkyl isocyanurates,        which represent cyclic trimers of the diisocyanates, or comprise        mixtures with their higher homologs containing more than one        isocyanurate ring. The isocyanato isocyanurates generally have        an NCO content of from 10 to 30% by weight, in particular from        15 to 25% by weight, and an average NCO functionality of from 3        to 4.5.    -   2) Uretdione diisocyanates containing aromatically,        aliphatically and/or cycloaliphatically bonded isocyanate        groups, preferably aliphatically and/or cycloaliphatically        bonded isocyanate groups, and being derived in particular from        hexamethylene diisocyanate or isophorone diisocyanate. Uretdione        diisocyanates are cyclic dimerization products of diisocyanates.        In the formulations of the invention, the uretdione        diisocyanates may be used as the sole component or in a mixture        with other polyisocyanates, especially those specified under 1).    -   3) Polyisocyanates containing biuret groups and aromatically,        cycloaliphatically or aliphatically bonded, preferably        cycloaliphatically or aliphatically bonded isocyanate groups,        especially tris(6-isocyanatohexyl)biuret or its mixtures with        its higher homologs. These polyisocyanates containing biruet        groups generally have an NCO content of from 18 to 22% by weight        and an average NCO functionality of from 3 to 4.5.    -   4) Polyisocyanates containing urethane and/or allophonate groups        and aromatically, aliphatically or cycloaliphatically bonded        isocyanate groups, preferably aliphatically or        cycloaliphatically bonded isocyanate groups, such as may be        obtained, for example, by reacting excess amounts of        hexamethylene diisocyanate or of isophorone diisocyanate with        polyhydric alcohols such as trimethylolpropane, neopentyl        glycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol,        1,3-propanediol, ethylene glycol, diethylene glycol, glycerol,        1,2-dihydroxypropane or mixtures thereof. These polyisocyanates        containing urethane and/or allophonate groups generally have an        NCO content of from 12 to 20% by weight and an average NCO        functionality of from 2.5 to 3.    -   5) Polyisocyanates containing oxadiazinetrione groups,        preferably derived from hexamethylene diisocyanate or isophorone        diisocyanate. Polyisocyanates of this kind containing        oxadiazinetrione groups may be prepared from diisocyanate and        carbon dioxide.    -   6) Uretonimine-modified polyisocyanates.

The polyisocyanates 1) to 6) may be used in a mixture, including ifdesired in a mixture with diisocyanates.

Suitable components b) include compounds which carry at least oneisocyanate-reactive group and at least one free-radically orcationically polymerizable group.

Isocyanate-reactive groups may, for example, be —OH, —SH, —NH₂ and—NHR⁴, R⁴ being as defined below, but may be different from the radicalsused there.

Polymerizable groups may be those containing unsaturated bonds,preferably carbon-carbon double bonds.

Examples of free-radically polymerizable groups are isolatedethylenically unsaturated groups, conjungated unsaturated groups,vinylaromatic groups, vinyl and vinylidene chloride-type groups,N-vinylamides, vinylpyrrolidones, vinyllactams, vinyl esters,(meth)acrylic esters or acrylonitriles.

Examples of cationically polymerizable groups are isobutylene units orvinyl ethers.

Components b) may, for example, be monoesters of α,β-unsaturatedcarboxylic acids, such as acrylic acid, methacrylic acid (referred tobelow for short as “(meth)acrylic acid”), crotonic acid, itaconic acid,fumaric acid, maleic acid, acrylamidoglycolic acid,methacrylamidoglycolic acid or vinyl ethers with diols or polyols whichpreferably have from 2 to 20 carbon atoms and at least two hydroxylgroups, such as ethylene glycol, diethylene glycol, triethylene glycol,1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol,dipropylene glycol, triethylene glycol, tetraethylene glycol,pentaethylene glycol, tripropylene glycol, 1,4-butanediol,1,5-pentanediol, neopentyl glycol, 1,6-hexanediol,2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol,1,4-dimethylolcyclohexane, glycerol, trimethylolethane,trimethylolpropane, trimethylolbutane, pentaerythritol,ditrimethylolpropane, erythritol, sorbitol, poly THF having a molarweight of between 162 and 378, poly-1,3-propanediol having a molarweight of between 134 and 400 or polyethylene glycol having a molarweight of between 238 and 458. Furthermore, it is also possible to useesters or amides of (meth)acrylic acid with amino alcohols, e.g.,2-aminoethanol, 2-(methylamino)ethanol, 3-amino-1-propanol,1-amino-2-propanol or 2-(2-aminoethoxy)ethanol, 2-mercaptoethanol orpolyaminoalkanes, such as ethylenediamine or diethylentriamine, orvinylacetic acid.

Furthermore, unsaturated polyetherols or polyesterols or polyacrylatepolyols having an average OH functionality of from 2 to 10 are suitable.

Examples of amides of ethylenically unsaturated carboxylic acids withamino aclohols are hydroxyalkyl(meth)acrylamides such asN-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide,N-hydroxyethylacrylamide, N-hydroyxethylmethacrylamide,5-hydroxy-3-oxapentyl(meth)acrylamide, N-hydroxyalkylcrotonamides suchas N-hydroxymethylcrotonamide or N-hydroxyalkylmaleimides such asN-hydroxyethylmaleimide.

Preference is given to using 2-hydroxyethyl(meth)acrylate, 2- or3-hydroxypropyl(meth)acrylate, 1,4-butanediol mono(meth)acrylate,neopentyl glycol mono(meth)acrylate, glycerol mono- anddi(meth)acrylate, trimethylolpropane mono- and di(meth)acrylate,pentaerythritol mono-, di- and tri(meth)acrylate and also 4-hydroxybutylvinyl ether, 2-aminoethyl(meth)acrylate, 2-aminopropyl(meth)acrylate,3-aminopropyl(meth)acrylate, 4-aminobutyl(meth)acrylate,6-aminohexyl(meth)acrylate, 2-thioethyl(meth)acrylate,2-aminoethyl(meth)acrylamide, 2-aminopropyl(meth)acrylamide,3-aminopropyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylamide,2-hydroxypropyl(meth)acrylamide or 3-hydroxypropyl(meth)acrylamide.Particular preference is given to 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate,1,4-butanediol monoacrylate, and 3-(acryloyloxy)-2-hydroxypropylmethacrylate.

Suitable components c) include compounds of the formulaR—O—(CO)—NH—R¹ orR—(NR¹)—(CO)—NH—R²where

-   -   R is an aliphatic, cycloaliphatic or aromatic radical of 2 to 20        carbon atoms which must contain at least one isocyanate-reactive        group, such as —OH, —NH₂, —NHR⁴ or —SH, and    -   R¹, R² and R⁴ independently of one another are hydrogen or an        alkyl group containing 1 to 4 carbon atoms.

Accordingly, a carbamate end group is in accordance with the invention acarbamic ester which is attached to the radical R via the oxygen atom,and not an unstable carbamic acid attached via the nitrogen atom.

R¹, R² and R⁴ therein may independently of one another be hydrogen,methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl ortert-butyl. Furthermore, R¹ and R² may also together form a ring inwhich R¹ and R² act as bridges, e.g. 1,2-ethylene, 1,2-propylene,1,3-propylene or 1,4-butylene.

R therein may have one of the following meanings: hydroxymethyl,2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl,4-hydroxybutyl, 6-hydroxyhexyl, 8-hydroxyoctyl, 10-hydroxydecyl,12-hydroxydodecyl, 2-hydroxycyclopentyl, 3-hydroxycyclopentyl,2-hydroxycyclohexyl, 3-hydroxycyclohexyl, 4-hydroxycyclohexyl,5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 7-hydroxy-4-oxaheptyl,3-hydroxy-2-ethylhexyl, 3-hydroxy-2,4-diethyloctyl,2,2-di(hydroxymethyl)butyl, 2,2-di(hydroxymethyl)propyl,2,2,2-tri(hydroxymethyl)ethyl, 2-hydroxymethyl-2,2-dimethylethyl,thiomethyl, 2-thioethyl, 2-thiopropyl, 3-thiopropyl, 2-thiobutyl,4-thiobutyl, 6-thiohexyl, 8-thiooctyl, 10-thiodecyl, 12-thiododecyl,2-thiocyclopentyl, 3-thiocyclopentyl, 2-thiocyclohexyl,3-thiocyclohexyl, 4-thiocyclohexyl, 5-thio-3-oxapentyl,8-thio-3,6-dioxaoctyl, 7-thio-4-oxaheptyl, 3-thio-2-ethylhexyl,3-thio-2,4-diethyloctyl, aminomethyl, 2-aminoethyl, 2-aminopropyl,3-aminopropyl, 2-aminobutyl, 4-aminobutyl, 6-aminohexyl, 8-aminooctyl,10-aminodecyl, 12-aminododecyl, 2-aminocyclopentyl, 3-aminocyclopentyl,2-aminocyclohexyl, 3-aminocyclohexyl, 4-aminocyclohexyl,5-amino-3-oxapentyl, 8-amino-3,6-dioxaoctyl, 7-amino-4-oxaheptyl,3-amino-2-ethylhexyl, 3-amino-2,4-diethyloctyl,3-amino-3,5,5-trimethylcyclohexyl, (n-methylamino)methyl,2-(N-methylamino)ethyl, 2-(N-methylamino)propyl,3-(N-methylamino)propyl, 2-(N-methylamino)butyl, 4-(N-methylamino)butyl,6-(N-methylamino)hexyl, 8-(N-methylamino)octyl, 10-(N-methylamino)decyl,12-(N-methylamino)dodecyl, 2-(N-methylamino)cyclopentyl,3-(N-methylamino)cyclopentyl, 2-(N-methylamino)cyclohexyl,3-(N-methylamino)cyclohexyl, 4-(N-methylamino)cyclohexyl,5-(N-methylamino)-3-oxapentyl, 8-(N-methylamino)-3,6-dioxaoctyl,7-(N-methylamino)-4-oxaheptyl, 3-(N-methylamino)-2-ethylhexyl,3-(N-methylamino)-2,4-diethyloctyl, (n-methylamino)methyl,2-(N-ethylamino)ethyl, 2-(N-ethylamino)propyl, 3-(N-ethylamino)propyl,2-(N-ethylamino)butyl, 4-(N-ethylamino)butyl, 6-(N-ethylamino)hexyl,8-(N-ethylamino)octyl, 10-(N-ethylamino)decyl, 12-(N-ethylamino)dodecyl,2-(N-ethylamino)cyclopentyl, 3-(N-ethylamino)cyclopentyl,2-(N-ethylamino)cyclohexyl, 3-(N-ethylamino)cyclohexyl,4-(N-ethylamino)cyclohexyl, 5-(N-ethylamino)-3-oxapentyl,8-(N-ethylamino)-3,6-dioxaoctyl, 7-(N-ethylamino)-4-oxaheptyl,3-(N-ethylamino)-2-ethylhexyl, 3-(N-ethylamino)-2,4-diethyloctyl,2-(N-butylamino)ethyl, 2-(N-butylamino)propyl, 3-(N-butylamino)propyl,2-(N-butylamino)butyl, 4-(N-butylamino)butyl, 6-(N-butylamino)hexyl,8-(N-butylamino)octyl, 10-(N-butylamino)decyl, 12-(N-butylamino)dodecyl,2-(N-butylamino)cyclopentyl, 3-(N-butylamino)cyclopentyl,2-(N-butylamino)cyclopentyl, 3-(N-butylamino)cyclohexyl,4-(N-butylamino)cyclohexyl, 5-(N-butylamino)-3-oxapentyl,8-(N-butylamino)-3,6-dioxaoctyl, 7-(N-butylamino)-4-oxaheptyl,3-(N-butylamino)-2-ethylhexyl or 3-(N-butylamino)-2,4-diethyloctyl.

Examples of compounds c) are the products of ring opening obtainable byreacting cyclic carbonates with ammonia or primary amines, or thoseaminocarbamates which are obtainable by reacting alkylene oxides withureas, as known, for example, from U.S. Pat. No. 2,842,523.

Further examples of compounds c) are O-(2-hydroxyethyl)carbamate,O-(2-hydroxypropyl)carbamate, O-(3-hydroxypropyl)carbamate,O-(4-hydroxybutyl)carbamate, O-(6-hydroxyhexyl)carbamate,O-(3-hydroxy-2-ethylhexyl) carbamate,O-(3-hydroxy-2,4-diethyloctyl)carbamate,O-(2,2-di(hydroxymethyl)butyl)carbamate,O-(2,2-di(hydroxymethyl)propyl)carbamate,O-(2,2,2-tri(hydroxymethyl)ethyl)carbamate,O-(2-hydroxymethyl-2,2-dimethylethyl)carbamate,O-(5-hydroxy-3-oxapentyl)carbamate, O-(8-hydroxy-3,6-dioxaoctyl)carbamate, O-(7-hydroxy-4-oxaheptyl)carbamate,O-(2-hydroxyethyl)N-methylcarbamate, O-(2-hydroxypropyl)N-methylcarbamate, O-(3-hydroxypropyl)N-methylcarbamate,O-(4-hydroxybutyl)N-methylcarbamate, O-(6-hydroxyhexyl)N-methylcarbamate, O-(3-hydroxy-2-ethylhexyl)N-methylcarbamate,O-(3-hydroxy-2,4-diethyloctyl)N-methylcarbamate,O-(2,2-di(hydroxymethyl)butyl)N-methylcarbamate,O-(2,2-di(hydroxymethyl)propyl)N-methylcarbamate,O-(2,2,2-tri(hydroxymethyl)ethyl)N-methylcarbamate,O-(2-hydroxymethyl-2,2-dimethylethyl)N-methylcarbamate,O-(5-hydroxy-3-oxapentyl)N-methylcarbamate,O-(8-hydroxy-3,6-dioxaoctyl)N-methylcarbamate,O-(7-hydroxy-4-oxaheptyl)N-methylcarbamate, O-(2-hydroxyethyl)N-ethylcarbamate, O-(2-hydroxypropyl)N-ethylcarbamate,O-(3-hydroxypropyl)N-ethylcarbamate, O-(4-hydroxybutyl)N-ethylcarbamate, O-(6-hydroxyhexyl)N-ethylcarbamate,O-(3-hydroxy-2-ethylhexyl)N-ethylcarbamate,O-(3-hydroxy-2,4-diethyloctyl)N-ethylcarbamate,O-(2,2-di(hydroxymethyl)butyl)N-ethylcarbamate,O-(2,2-di(hydroxymethyl)propyl)N-ethylcarbamate,O-(2,2,2-tri(hydroxymethyl)ethyl)N-ethylcarbamate,O-(2-hydroxymethyl-2,2-dimethylethyl)N-ethylcarbamate,O-(5-hydroxy-3-oxapentyl)N-ethylcarbamate,O-(8-hydroxy-3,6-dioxaoctyl)N-ethylcarbamate,O-(7-hydroxy-4-oxaheptyl)N-ethylcarbamate, O-(2-hydroxyethyl)N-butylcarbamate, O-(2-hydroxypropyl)N-butylcarbamate,O-(3-hydroxypropyl)N-butylcarbamate, O-(4-hydroxybutyl)N-butylcarbamate, O-(6-hydroxyhexyl)N-butylcarbamate,O-(3-hydroxy-2-ethylhexyl)N-butylcarbamate,O-(3-hydroxy-2,4-diethyloctyl)N-butylcarbamate,O-(2,2-di(hydroxymethyl)butyl)N-butylcarbamate,O-(2,2-di(hydroxymethyl)propyl)N-butylcarbamate,O-(2,2,2-tri(hydroxymethyl)ethyl)N-butylcarbamate,O-(2-hydroxymethyl-2,2-dimethylethyl)N-butylcarbamate,O-(5-hydroxy-3-oxapentyl)N-butylcarbamate,O-(8-hydroxy-3,6-dioxaoctyl)N-butylcarbamate,O-(7-hydroxy-4-oxaheptyl)N-butylcarbamate,O-(2-(methylamino)ethyl)carbamate, O-(2-(methylamino)propyl) carbamate,O-(3-(methylamino)propyl)carbamate, O-(4-(methylamino)butyl)carbamate,O-(6-(methylamino)hexyl) carbamate,O-(3-(methylamino)-2-ethylhexyl)carbamate,O-(3-(methylamino)-2,4-diethyloctyl)carbamate,O-(2,2-di((methylamino)methyl)butyl)carbamate,O-(2,2-di((methylamino)methyl)propyl)carbamate,O-(2,2,2-tri((methylamino)methyl)ethyl)carbamate,O-(2-(methylamino)methyl-2,2-dimethylethyl)carbamate,O-(5-methylamino-3-oxapentyl)carbamate,O-(8-methylamino-3,6-dioxaoctyl)carbamate,O-(7-methylamino-4-oxaheptyl)carbamate, O-(2-(methylamino)ethyl)N-methylcarbamate, O-(2-(methylamino)propyl)N-methylcarbamate,O-(3-(methylamino)propyl)N-methylcarbamate,O-(4-(methylamino)butyl)N-methylcarbamate,O-(6-(methylamino)hexyl)N-methylcarbamate,O-(3-methylamino-2-ethylhexyl)N-methylcarbamate,O-(3-methylamino-2,4-diethyloctyl)N-methylcarbamate,O-(2,2-di((methylamino)methyl)butyl)N-methylcarbamate,O-(2,2-di((methylamino)methyl)propyl)N-methylcarbamate,O-(2,2,2-tri((methylamino)methyl)ethyl)N-methylcarbamate,O-(2-(methylamino)methyl-2,2-dimethylethyl)N-methylcarbamate,O-(5-methylamino-3-oxapentyl)N-methylcarbamate,O-(8-methylamino-3,6-dioxaoctyl)N-methylcarbamate,O-(7-methylamino-4-oxaheptyl)N-methylcarbamate,O-(2-(methylamino)ethyl)N-ethylcarbamate,O-(2-(methylamino)propyl)N-ethylcarbamate,O-(3-(methylamino)propyl)N-ethylcarbamate,O-(4-(methylamino)butyl)N-ethylcarbamate,O-(6-(methylamino)hexyl)N-ethylcarbamate,O-(3-methylamino-2-ethylhexyl)N-ethylcarbamate,O-(3-methylamino-2,4-diethyloctyl)N-ethylcarbamate,O-(2,2-di((methylamino)methyl)butyl)N-ethylcarbamate,O-(2,2-di((methylamino)methyl)propyl)N-ethylcarbamate,O-(2,2,2-tri((methylamino)methyl)ethyl)N-ethylcarbamate,O-(2-(methylamino)methyl-2,2-dimethylethyl)N-ethylcarbamate,O-(5-methylamino-3-oxapentyl)N-ethylcarbamate,O-(8-methylamino-3,6-dioxaoctyl)N-ethylcarbamate,O-(7-methylamino-4-oxaheptyl)N-ethylcarbamate,O-(2-(methylamino)ethyl)N-butylcarbamate,O-(2-(methylamino)propyl)N-butylcarbamate,O-(3-(methylamino)propyl)N-butylcarbamate,O-(4-(methylamino)butyl)N-butylcarbamate,O-(6-(methylamino-2)hexyl)N-butylcarbamate,O-(3-methylamino-2-ethylhexyl)N-butylcarbamate,O-(3-methylamino-2,4-diethyloctyl)N-butylcarbamate,O-(2,2-di((methylamino)methyl)butyl)N-butylcarbamate,O-(2,2-di((methylamino)methyl)propyl)N-butylcarbamate,O-(2,2,2-tri((methylamino)methyl)ethyl)N-butylcarbamate,O-(2-(methylamino)methyl-2,2-dimethylethyl)N-butylcarbamate,O-(5-methylamino-3-oxapentyl)N-butylcarbamate,O-(8-methylamino-3,6-dioxaoctyl)N-butylcarbamate,O-(7-methylamino-4-oxaheptyl)N-butylcarbamate,O-(2-(ethylamino)ethyl)carbamate, O-(2-(ethylamino)propyl) carbamate,O-(3-(ethylamino)propyl)carbamate, O-(4-(ethylamino)butyl)carbamate,O-(6-(ethylamino)hexyl) carbamate,O-(3-ethylamino-2-ethylhexyl)carbamate,O-(3-ethylamino-2,4-diethyloctyl)carbamate,O-(2,2-di((ethylamino)methyl)butyl)carbamate,O-(2,2-di((ethylamino)methyl)propyl)carbamate,O-(2,2,2-tri((ethylamino)methyl)ethyl)carbamate,O-(2-(ethylamino)methyl-2,2-dimethylethyl)carbamate,O-(5-ethylamino-3-oxapentyl)carbamate,O-(8-ethylamino-3,6-dioxaoctyl)carbamate,O-(7-ethylamino-4-oxaheptyl)carbamate, O-(2-(ethylamino)ethyl)N-methylcarbamate, O-(2-(ethylamino)propyl)N-methylcarbamate,O-(3-(ethylamino)propyl)N-methylcarbamate,O-(4-(ethylamino)butyl)N-methylcarbamate,O-(6-(ethylamino)hexyl)N-methylcarbamate,O-(3-ethylamino-2-ethylhexyl)N-methylcarbamate,O-(3-ethylamino-2,4-diethyloctyl)N-methylcarbamate,O-(2,2-di((ethylamino)methyl)butyl)N-methylcarbamate,O-(2,2-di((ethylamino)methyl)propyl)N-methylcarbamate,O-(2,2,2-tri((ethylamino)methyl)ethyl)N-methylcarbamate,O-(2-(ethylamino)methyl-2,2-dimethylethyl)N-methylcarbamate,O-(5-ethylamino-3-oxapentyl)N-methylcarbamate,O-(8-ethylamino-3,6-dioxaoctyl)N-methylcarbamate,O-(7-ethylamino-4-oxaheptyl)N-methylcarbamate,O-(2-(ethylamino)ethyl)N-ethylcarbamate,O-(2-(ethylamino)propyl)N-ethylcarbamate,O-(3-(ethylamino)propyl)N-ethylcarbamate,O-(4-(ethylamino)butyl)N-ethylcarbamate, O-(6-(ethylamino)hexyl)N-ethylcarbamate, O-(3-ethylamino-2-ethylhexyl)N-ethylcarbamate,O-(2,2-di((ethylamino)methyl)butyl)N-ethylcarbamate,O-(2,2-di((ethylamino)methyl)propyl)N-ethylcarbamate,O-(2,2,2-tri((ethylamino)methyl)ethyl)N-ethylcarbamate,O-(2-(ethylamino)methyl-2,2-dimethylethyl)N-ethylcarbamate,O-(5-ethylamino-3-oxapentyl)N-ethylcarbamate,O-(8-ethylamino-3,6-dioxaoctyl)N-ethylcarbamate,O-(7-ethylamino-4-oxaheptyl)N-ethylcarbamate,O-(2-(ethylamino)ethyl)N-butylcarbamate,O-(2-(ethylamino)propyl)N-butylcarbamate,O-(3-(ethylamino)propyl)N-butylcarbamate,O-(4-(ethylamino)butyl)N-butylcarbamate, O-(6-(ethylamino)hexyl)N-butylcarbamate, O-(3-ethylamino-2-ethylhexyl)N-butylcarbamate,O-(3-ethylamino-2,4-diethyloctyl)N-butylcarbamate,O-(2,2-di((ethylamino)methyl)butyl)N-butylcarbamate,O-(2,2-di((ethylamino)methyl)propyl)N-butylcarbamate,O-(2,2,2-tri((ethylamino)methyl)ethyl)N-butylcarbamate,O-(2-(ethylamino)methyl-2,2-dimethylethyl)N-butylcarbamate,O-(5-ethylamino-3-oxapentyl)N-butylcarbamate,O-(8-ethylamino-3,6-dioxaoctyl)N-butylcarbamate,O-(7-ethylamino-4-oxaheptyl)N-butylcarbamate,O-(2-(butylamino)ethyl)carbamate, O-(2-(butylamino)propyl) carbamate,O-(3-(butylamino)propyl)carbamate, O-(4-(butylamino)butyl)carbamate,O-(6-(butylamino)hexyl) carbamate,O-(3-butylamino-2-ethylhexyl)carbamate,O-(3-butylamino-2,4-diethyloctyl)carbamate,O-(2,2-di((butylamino)methyl)butyl)carbamate,O-(2,2-di((butylamino)methyl)propyl)carbamate,O-(2,2,2-tri((butylamino)methyl)ethyl)carbamate,O-(2-(butylamino)methyl-2,2-dimethylethyl)carbamate,O-(5-butylamino-3-oxapentyl)carbamate,O-(8-butylamino-3,6-dioxaoctyl)carbamate,O-(7-butylamino-4-oxaheptyl)carbamate, O-(2-(butylamino)ethyl)N-methylcarbamate, O-(2-(butylamino)propyl)N-methylcarbamate,O-(3-(butylamino)propyl)N-methylcarbamate,O-(4-(butylamino)butyl)N-methylcarbamate,O-(6-(butylamino)hexyl)N-methylcarbamate,O-(3-butylamino-2-ethylhexyl)N-methylcarbamate,O-(3-butylamino-2,4-diethyloctyl)N-methylcarbamate,O-(2,2-di((butylamino)methyl)butyl)N-methylcarbamate,O-(2,2-di((butylamino)methyl)propyl)N-methylcarbamate,O-(2,2,2-tri((butylamino)methyl)ethyl)N-methylcarbamate,O-(2-(butylamino)methyl-2,2-dimethylethyl)N-methylcarbamate,O-(5-butylamino-3-oxapentyl)N-methylcarbamate,O-(8-butylamino-3,6-dioxaoctyl)N-methylcarbamate,O-(7-butylamino-4-oxaheptyl)N-methylcarbamate,O-(2-(butylamino)ethyl)N-ethylcarbamate,O-(2-(butylamino)propyl)N-ethylcarbamate,O-(3-(butylamino)propyl)N-ethylcarbamate,O-(4-(butylamino)butyl)N-ethylcarbamate, O-(6-(butylamino)hexyl)N-ethylcarbamate, O-(3-butylamino-2-ethylhexyl)N-ethylcarbamate,O-(3-butylamino-2,4-diethyloctyl)N-ethylcarbamate,O-(2,2-di((butylamino)methyl)butyl)N-ethylcarbamate,O-(2,2-di((butylamino)methyl)propyl)N-ethylcarbamate,O-(2,2,2-tri((butylamino)methyl)ethyl)N-ethylcarbamate,O-(2-(butylamino)methyl-2,2-dimethylethyl)N-ethylcarbamate,O-(5-butylamino-3-oxapentyl)N-ethylcarbamate,O-(8-butylamino-3,6-dioxaoctyl)N-ethylcarbamate,O-(7-butylamino-4-oxaheptyl)N-ethylcarbamate,O-(2-(butylamino)ethyl)N-butylcarbamate,O-(2-(butylamino)propyl)N-butylcarbamate,O-(3-(butylamino)propyl)N-butylcarbamate,O-(4-(butylamino)butyl)N-butylcarbamate, O-(6-(butylamino)hexyl)N-butylcarbamate, O-(3-butylamino-2-ethylhexyl)N-butylcarbamate,O-(3-butylamino-2,4-diethyloctyl)N-butylcarbamate,O-(2,2-di((butylamino)methyl)butyl)N-butylcarbamate,O-(2,2-di((butylamino)methyl)propyl)N-butylcarbamate,O-(2,2,2-tri((butylamino)methyl)ethyl)N-butylcarbamate,O-(2-(butylamino)methyl-2,2-dimethylethyl)N-butylcarbamate,O-(5-butylamino-3-oxapentyl)N-butylcarbamate,O-(8-butylamino-3,6-dioxaoctyl)N-butylcarbamate,O-(7-butylamino-4-oxaheptyl)N-butylcarbamate, O-(2-thioethyl) carbamate,O-(2-thiopropyl)carbamate, O-(3-thiopropyl) carbamate,O-(4-thiobutyl)carbamate, O-(6-thiohexyl)carbamate,O-(2-thioethyl)N-methylcarbamate, O-(2-thiopropyl) N-methylcarbamate,O-(3-thiopropyl)N-methylcarbamate, O-(4-thiobutyl)N-methylcarbamate,O-(6-thiohexyl) N-methylcarbamate, O-(2-thioethyl)N-ethylcarbamate,O-(2-thiopropyl)N-ethylcarbamate, O-(3-thiopropyl) N-ethylcarbamate,O-(4-thiobutyl)N-ethylcarbamate, O-(6-thiohexyl)N-ethylcarbamate,O-(2-thioethyl) N-butylcarbamate, O-(2-thiopropyl)N-butylcarbamate,O-(3-thiopropyl)N-butylcarbamate, O-(4-thiobutyl) N-butylcarbamate,O-(6-thiohexyl)N-butylcarbamate, N-(2-hydroxyethyl)urea,N-(2-hydroxypropyl)urea, N-(3-hydroxypropyl)urea,N-(4-hydroxybutyl)urea, N-(6-hydroxyhexyl)urea,N-(3-hydroxy-2-ethylhexyl)urea, N-(3-hydroxy-2,4-diethyloctyl)urea,N-(2,2-di(hydroxymethyl)butyl)urea, N-(2,2-di(hydroxymethyl)propyl)urea,N-(2,2,2-tri(hydroxymethyl)ethyl)urea,N-(2-hydroxymethyl-2,2-dimethylethyl)urea,N-(5-hydroxy-3-oxapentyl)urea, N-(8-hydroxy-3,6-dioxaoctyl)urea,N-(7-hydroxy-4-oxaheptyl)urea,N-(3-amino-3,5,5-trimethylcyclohexyl)-urea,N-(3-hydroxy-3,5,5-trimethylcyclohexyl)urea, N-(2-hydroxyethyl)N′-methylurea, N-(2-hydroxypropyl)-N′-methylurea,N-(3-hydroxypropyl)-N′-methylurea, N-(4-hydroxybutyl)-N′-methylurea,N-(6-hydroxyhexyl)-N′-methylurea,N-(3-hydroxy-2-ethylhexyl)-N′-methylurea,N-(3-hydroxy-2,4-diethyl-octyl)-N′-methylurea,N-(2,2-di(hydroxymethyl)butyl)-N′-methylurea,N-(2,2-di(hydroxymethyl)propyl)-N′-methylurea,N-(2,2,2-tri(hydroxymethyl)ethyl)-N′-methylurea,N-(2-hydroxymethyl-2,2-dimethylethyl)-N′-methylurea,N-(5-hydroxy-3-oxapentyl)-N′-methylurea,N-(8-hydroxy-3,6-dioxaoctyl)-N′-methylurea,N-(7-hydroxy-4-oxaheptyl)-N′-methylurea,N-(3-amino-3,5,5-trimethylcyclohexyl)-N′-methylurea,N-(3-hydroxy-3,5,5-trimethylcyclohexyl)-N′-methylurea,N-(2-hydroxyethyl)-N′-ethylurea, N-(2-hydroxypropyl)-N′-ethylurea,N-(3-hydroxypropyl)-N′-ethylurea, N-(4-hydroxybutyl)-N′-ethylurea,N-(6-hydroxyhexyl)-N′-ethylurea,N-(3-hydroxy-2-ethylhexyl)-N′-ethylurea,N-(3-hydroxy-2,4-diethyloctyl)-N′-ethylurea,N-(2,2-di(hydroxymethyl)butyl)-N′-ethylurea,N-(2,2-di(hydroxymethyl)propyl)-N′-ethylurea,N-(2,2,2-tri(hydroxymethyl)ethyl)-N′-ethylurea,N-(2-hydroxymethyl-2,2-dimethylethyl)-N′-ethylurea,N-(5-hydroxy-3-oxapentyl)-N′-ethylurea,N-(8-hydroxy-3,6-dioxaoctyl)-N′-ethylurea,N-(7-hydroxy-4-oxaheptyl)-N′-ethylurea,N-(3-amino-3,5,5-trimethylcyclohexyl)-N′-ethylurea,N-(3-hydroxy-3,5,5-trimethylcyclohexyl)-N′-ethylurea,N-(2-hydroxyethyl)-N′-butylurea, N-(2-hydroxypropyl)-N′-butylurea,N-(3-hydroxypropyl)-N′-butylurea, N-(4-hydroxybutyl)-N′-butylurea,N-(6-hydroxyhexyl)-N′-butylurea,N-(3-hydroxy-2-ethyl-hexyl)-N′-butylurea,N-(3-hydroxy-2,4-diethyloctyl)-N′-butylurea,N-(2,2-di(hydroxymethyl)butyl)-N′-butylurea,N-(2,2-di(hydroxymethyl)propyl)-N′-butylurea,N-(2,2,2-tri(hydroxymethyl)ethyl)-N′-butylurea,N-(2-hydroxymethyl-2,2-dimethylethyl)-N′-butylurea,N-(5-hydroxy-3-oxapentyl)-N′-butylurea,N-(8-hydroxy-3,6-dioxaoctyl)-N′-butylurea,N-(7-hydroxy-4-oxaheptyl)-N′-butylurea,N-(3-amino-3,5,5-trimethylcyclohexyl)-N′-butylurea,N-(3-hydroxy-3,5,5-trimethylcyclohexyl)-N′-butylurea,N-(2-(methylamino)ethyl)urea, N-(2-(methylamino)propyl)urea,N-(3-(methylamino)propyl)urea, N-(4-(methylamino)butyl)urea,N-(6-(methylamino)hexyl)urea, N-(3-methylamino-2-ethylhexyl)urea,N-(3-methylamino-2,4-diethyloctyl)urea,N-(2,2-di((methylamino)methyl)butyl)urea,N-(2,2-di((methylamino)methyl)propyl)urea,N-(2,2,2-tri((methylamino)methyl)ethyl)urea,N-(2-(methylamino)methyl-2,2-dimethylethyl)urea,N-(5-methylamino-3-oxapentyl)urea, N-(8-methylamino-3,6-dioxaoctyl)urea,N-(7-methylamino-4-oxaheptyl)urea,N-(2-(methylamino)ethyl)-N′-methylurea,N-(2-(methylamino)propyl)-N′-methylurea,N-(3-(methylamino)propyl)-N′-methylurea,N-(4-(methylamino)butyl)-N′-methylurea,N-(6-(methylamino)hexyl)-N′-methylurea,N-(3-methylamino-2-ethylhexyl)-N′-methylurea,N-(3-methylamino-2,4-diethyloctyl)-N′-methylurea,N-(2,2-di((methylamino)methyl)butyl)-N′-methylurea,N-(2,2-di((methylamino)methyl)propyl)-N′-methylurea,N-(2,2,2-tri((methylamino)methyl)ethyl)-N′-methylurea,N-(2-(methylamino)methyl-2,2-dimethylethyl)-N′-methylurea,N-(5-methylamino-3-oxapentyl)-N′-methylurea,N-(8-methylamino-3,6-dioxaoctyl)-N′-methylurea,N-(7-methylamino-4-oxaheptyl)-N′-methylurea,N-(2-(methylamino)ethyl)-N′-ethylurea,N-(2-(methylamino)propyl)-N′-ethylurea,N-(3-(methylamino)propyl)-N′-ethylurea,N-(4-(methylamino)butyl)-N′-ethylurea,N-(6-(methylamino)hexyl)-N′-ethylurea,N-(3-methylamino-2-ethylhexyl)-N′-ethylurea,N-(3-methylamino-2,4-diethyloctyl)-N′-ethylurea,N-(2,2-di((methylamino)methyl)butyl)-N′-ethylurea,N-(2,2-di((methylamino)methyl)propyl)-N′-ethylurea,N-(2,2,2-tri((methylamino)methyl)ethyl)-N′-ethylurea,N-(2-(methylamino)methyl-2,2-dimethylethyl)-N′-ethylurea,N-(5-methylamino-3-oxapentyl)-N′-ethylurea,N-(8-methylamino-3,6-dioxaoctyl)-N′-ethylurea,N-(7-methylamino-4-oxaheptyl)-N′-ethylurea,N-(2-(methylamino)ethyl)-N′-butylurea,N-(2-(methylamino)propyl)-N′-butylurea,N-(3-(methylamino)propyl)-N′-butylurea,N-(4-(methylamino)butyl)-N′-butylurea,N-(6-(methylamino)hexyl)-N′-butylurea,N-(3-methylamino-2-ethylhexyl)-N′-butylurea,N-(3-methylamino-2,4-diethyloctyl)-N′-butylurea,N-(2,2-di((methylamino)methyl)butyl)-N′-butylurea,N-(2,2-di((methylamino)methyl)propyl)-N′-butylurea,N-(2,2,2-tri((methylamino)methyl)ethyl)-N′-butylurea,N-(2-(methylamino)methyl-2,2-dimethylethyl)-N′-butylurea,N-(5-methylamino-3-oxapentyl)-N′-butylurea,N-(8-methylamino-3,6-dioxaoctyl)-N′-butylurea,N-(7-methylamino-4-oxaheptyl)-N′-butylurea, N-(2-(ethylamino)ethyl)urea,N-(2-(ethylamino)propyl)urea, N-(3-(ethylamino)propyl)urea,N-(4-(ethylamino)butyl)urea, N-(6-(ethylamino)hexyl)urea,N-(3-ethylamino-2-ethylhexyl)urea,N-(3-ethylamino-2,4-diethyloctyl)urea,N-(2,2-di((ethylamino)methyl)butyl)urea,N-(2,2-di((ethylamino)methyl)propyl)urea,N-(2,2,2-tri((ethylamino)methyl)ethyl)urea,N-(2-(ethylamino)methyl-2,2-dimethylethyl)urea,N-(5-ethylamino-3-oxapentyl)urea, N-(8-ethylamino-3,6-dioxaoctyl)urea,N-(7-ethylamino-4-oxaheptyl)urea, N-(2-(ethylamino)ethyl)-N′-methylurea,N-(2-(ethylamino)propyl)-N′-methylurea,N-(3-(ethylamino)propyl)-N′-methylurea,N-(4-(ethylamino)butyl)-N′-methylurea,N-(6-(ethylamino)hexyl)-N′-methylurea,N-(3-ethylamino-2-ethylhexyl)-N′-methylurea,N-(3-ethylamino-2,4-diethyloctyl)-N′-methylurea,N-(2,2-di((ethylamino)methyl)butyl)-N′-methylurea,N-(2,2-di((ethylamino)methyl)propyl)-N′-methylurea,N-(2,2,2-tri((ethylamino)methyl)ethyl)-N′-methylurea,N-(2-(ethylamino)methyl-2,2-dimethylethyl)-N′-methylurea,N-(5-ethylamino-3-oxapentyl)-N′-methylurea,N-(8-ethylamino-3,6-dioxaoctyl)-N′-methylurea,N-(7-ethylamino-4-oxaheptyl)-N′-methylurea,N-(2-(ethylamino)ethyl)-N′-ethylurea,N-(2-(ethylamino)propyl)-N′-ethylurea,N-(3-(ethylamino)propyl)-N′-ethylurea,N-(4-(ethylamino)butyl)-N′-ethylurea,N-(6-(ethylamino)hexyl)-N′-ethylurea,N-(3-ethylamino-2-ethylhexyl)-N′-ethylurea,N-(3-ethylamino-2,4-diethyloctyl)-N′-ethylurea,N-(2,2-di((ethylamino)methyl)butyl)-N′-ethylurea,N-(2,2-di((ethylamino)methyl)propyl)-N′-ethylurea,N-(2,2,2-tri((ethylamino)methyl)ethyl)-N′-ethylurea,N-(2-(ethylamino)methyl-2,2-dimethylethyl)-N′-ethylurea,N-(5-ethylamino-3-oxapentyl)-N′-ethylurea,N-(8-ethylamino-3,6-dioxaoctyl)-N′-ethylurea,N-(7-ethylamino-4-oxaheptyl)-N′-ethylurea,N-(2-(ethylamino)ethyl)-N′-butylurea,N-(2-(ethylamino)propyl)-N′-butylurea, N-(3-ethylamino)-N′-butylurea,N-(4-(ethylamino)butyl)-N′-butylurea,N-(6-(ethylamino)hexyl)-N′-butylurea,N-(3-ethylamino-2-ethylhexyl)-N′-butylurea,N-(3-ethylamino-2,4-diethyloctyl)-N′-butylurea,N-(2,2-di((ethylamino)methyl)butyl)-N′-butylurea,N-(2,2-di((ethylamino)methyl)propyl)-N′-butylurea,N-(2,2,2-tri((ethylamino)methyl)ethyl)-N′-butylurea,N-(2-(ethylamino)methyl-2,2-dimethylethyl)-N′-butylurea,N-(5-ethylamino-3-oxapentyl)-N′-butylurea,N-(8-ethylamino-3,6-dioxaoctyl)-N′-butylurea,N-(7-ethylamino-4-oxaheptyl)-N′-butylurea, N-(2-(butylamino)ethyl)urea,N-(2-(butylamino)propyl)urea, N-(3-(butylamino)propyl)urea,N-(4-(butylamino)butyl)urea, N-(6-(butylamino)hexyl)urea,N-(3-butylamino-2-ethylhexyl)urea,N-(3-butylamino-2,4-diethyloctyl)urea,N-(2,2-di((butylamino)methyl)butyl)urea,N-(2,2-di((butylamino)methyl)propyl)urea,N-(2,2,2-tri((butylamino)methyl)ethyl)urea,N-(2-(butylamino)methyl-2,2-dimethylethyl)urea,N-(5-butylamino-3-oxapentyl)urea, N-(8-butylamino-3,6-dioxaoctyl)urea,N-(7-butylamino-4-oxaheptyl)urea, N-(2-(butylamino)ethyl)-N′-methylurea,N-(2-(butylamino)propyl)-N′-methylurea,N-(3-(butylamino)propyl)-N′-methylurea,N-(4-(butylamino)butyl)-N′-methylurea,N-(6-(butylamino)hexyl)-N′-methylurea,N-(3-butylamino-2-ethylhexyl)-N′-methylurea,N-(3-butylamino-2,4-diethyloctyl)-N′-methylurea,N-(2,2-di((butylamino)methyl)butyl)-N′-methylurea,N-(2,2-di((butylamino)methyl)propyl)-N′-methylurea,N-(2,2,2-tri((butylamino)methyl)ethyl)-N′-methylurea,N-(2-(butylamino)methyl-2,2-dimethylethyl)-N′-methylurea,N-(5-butylamino-3-oxapentyl)-N′-methylurea,N-(8-butylamino-3,6-dioxaoctyl)-N′-methylurea,N-(7-butylamino-4-oxaheptyl)-N′-methylurea,N-(2-(butylamino)ethyl)-N′-ethylurea,N-(2-(butylamino)propyl)-N′-ethylurea,N-(3-(butylamino)propyl)-N′-ethylurea,N-(4-(butylamino)butyl)-N′-ethylurea,N-(6-(butylamino)hexyl)-N′-ethylurea,N-(3-butylamino-2-ethylhexyl)-N′-ethylurea,N-(3-butylamino-2,4-diethyloctyl)-N′-ethylurea,N-(2,2-di((butylamino)methyl)butyl)-N′-ethylurea,N-(2,2-di((butylamino)methyl)propyl)-N′-ethylurea,N-(2,2,2-tri((butylamino)methyl)ethyl)-N′-ethylurea,N-(2-(butylamino)methyl-2,2-dimethylethyl)-N′-ethylurea,N-(5-butylamino-3-oxapentyl)-N′-ethylurea,N-(8-butylamino-3,6-dioxaoctyl)-N′-ethylurea,N-(7-butylamino-4-oxaheptyl)-N′-ethylurea,N-(2-(butylamino)ethyl)-N′-butylurea,N-(2-(butylamino)propyl)-N′-butylurea,N-(3-(butylamino)propyl)-N′-butylurea,N-(4-(butylamino)butyl)-N′-butylurea,N-(6-(butylamino)hexyl)-N′-butylurea,N-(3-butylamino-2-ethylhexyl)-N′-butylurea,N-(3-butylamino-2,4-diethyloctyl)-N′-butylurea,N-(2,2-di((butylamino)methyl)butyl)-N′-butylurea,N-(2,2-di((butylamino)methyl)propyl)-N′-butylurea,N-(2,2,2-tri((butylamino)methyl)ethyl)-N′-butylurea,N-(2-(butylamino)methyl-2,2-dimethylethyl)-N′-butylurea,N-(5-butylamino-3-oxapentyl)-N′-butylurea,N-(8-butylamino-3,6-dioxaoctyl)-N′-butylurea,N-(7-butylamino-4-oxaheptyl)-N′-butylurea, N-(2-thioethyl)urea,N-(2-thiopropyl)urea, N-(3-thiopropyl)urea, N-(4-thiobutyl)urea,N-(6-thiohexyl)urea, N-(2-thioethyl)-N′-methylurea,N-(2-thiopropyl)-N′-methylurea, N-(3-thiopropyl)-N′-methylurea,N-(4-thiobutyl)-N′-methylurea, N-(6-thiohexyl)-N′-methylurea,N-(2-thioethyl)-N′-ethylurea, N-(2-thiopropyl)-N′-ethylurea,N-(3-thiopropyl)-N′-ethylurea, N-(4-thiobutyl)-N′-ethylurea,N-(6-thiohexyl)-N′-ethylurea, N-(2-thioethyl)-N′-butylurea,N-(2-thiopropyl)-N′-butylurea, N-(3-thiopropyl)-N′-butylurea,N-(4-thiobutyl)-N′-butylurea, N-(6-thiohexyl)-N′-butylurea,N-(2-hydroxyethyl)-N,N′-ethyleneurea,N-(2-hydroxypropyl)-N,N′-ethyleneurea,N-(3-hydroxypropyl)-N,N′-ethyleneurea,N-(4-hydroxybutyl)-N,N′-ethyleneurea,N-(6-hydroxyhexyl)-N,N′-ethyleneurea,N-(3-hydroxy-2-ethylhexyl)-N,N′-ethyleneurea,N-(3-hydroxy-2,4-diethyloctyl)-N,N′-ethyleneurea,N-(2,2-di(hydroxymethyl)butyl)-N,N′-ethyleneurea,N-(2,2-di(hydroxymethyl)propyl)-N,N′-ethyleneurea,N-(2,2,2-tri(hydroxymethyl)ethyl)-N,N′-ethyleneurea,N-(2-hydroxymethyl-2,2-dimethylethyl)-N,N′-ethyleneurea,N-(5-hydroxy-3-oxapentyl)-N,N′-ethyleneurea,N-(8-hydroxy-3,6-dioxaoctyl)-N,N′-ethyleneurea,N-(7-hydroxy-4-oxaheptyl)-N,N′-ethyleneurea,N-(2-(methylamino)ethyl)-N,N′-ethyleneurea,N-(2-(methylamino)propyl)-N,N′-ethyleneurea,N-(3-(methylamino)propyl)-N,N′-ethyleneurea,N-(4-(methylamino)butyl)-N,N′-ethyleneurea,N-(6-(methylamino)hexyl)-N,N′-ethyleneurea,N-(3-methylamino-2-ethylhexyl)-N,N′-ethyleneurea,N-(3-methylamino-2,4-diethyloctyl)-N,N′-ethyleneurea,N-(2,2-di((methylamino)methyl)butyl)-N,N′-ethyleneurea,N-(2,2-di((methylamino)methyl)propyl)-N,N′-ethyleneurea,N-(2,2,2-tri((methylamino)methyl)ethyl)-N,N′-ethyleneurea,N-(2-(methylamino)methyl-2,2-dimethylethyl)-N,N′-ethyleneurea,N-(5-methylamino-3-oxapentyl)-N,N′-ethyleneurea,N-(8-methylamino-3,6-dioxaoctyl)-N,N′-ethyleneurea,N-(7-methylamino-4-oxaheptyl)-N,N′-ethyleneurea,N-(3-amino-3,5,5-trimethylcyclohexyl)-N,N′-ethyleneurea,N-(3-hydroxy-3,5,5-trimethylcyclohexyl)-N,N′-ethyleneurea,N-(2-(ethylamino)ethyl)-N,N′-ethyleneurea,N-(2-(ethylamino)propyl)-N,N′-ethyleneurea,N-(3-(ethylamino)propyl)-N,N′-ethyleneurea,N-(4-(ethylamino)butyl)-N,N′-ethyleneurea,N-(6-(ethylamino)hexyl)-N,N′-ethyleneurea,N-(3-ethylamino-2-ethylhexyl)-N,N′-ethyleneurea,N-(3-ethylamino-2,4-diethyloctyl)-N,N′-ethyleneurea,N-(2,2-di((ethylamino)methyl)butyl)-N,N′-ethyleneurea,N-(2,2-di((ethylamino)methyl)propyl)-N,N′-ethyleneurea,N-(2,2,2-tri((ethylamino)methyl)ethyl)-N,N′-ethyleneurea,N-(2-(ethylamino)methyl-2,2-dimethylethyl)-N,N′-ethyleneurea,N-(5-ethylamino-3-oxapentyl)-N,N′-ethyleneurea,N-(8-ethylamino-3,6-dioxaoctyl)-N,N′-ethyleneurea,N-(7-ethylamino-4-oxaheptyl)-N,N′-ethyleneurea,N-(2-(butylamino)ethyl)-N,N′-ethyleneurea,N-(2-(butylamino)propyl)-N,N′-ethyleneurea,N-(3-(butylamino)propyl)-N,N′-ethyleneurea,N-(4-(butylamino)butyl)-N,N′-ethyleneurea,N-(6-(butylamino)hexyl)-N,N′-ethyleneurea,N-(3-butylamino-2-ethylhexyl)-N,N′-ethyleneurea,N-(3-butylamino-2,4-diethyloctyl)-N,N′-ethyleneurea,N-(2,2-di((butylamino)methyl)butyl)-N,N′-ethyleneurea,N-(2,2-di((butylamino)methyl)propyl)-N,N′-ethyleneurea,N-(2,2,2-tri((butylamino)methyl)ethyl)-N,N′-ethyleneurea,N-(2-(butylamino)methyl-2,2-dimethylethyl)-N,N′-ethyleneurea,N-(5-butylamino-3-oxapentyl)-N,N′-ethyleneurea,N-(8-butylamino-3,6-dioxaoctyl)-N,N′-ethyleneurea,N-(7-butylamino-4-oxaheptyl)-N,N′-ethyleneurea,N-(2-thioethyl)-N,N′-ethyleneurea, N-(2-thiopropyl)-N,N′-ethyleneurea,N-(3-thiopropyl)-N,N′-ethyleneurea, N-(4-thiobutyl)-N,N′-ethyleneurea,N-(6-thiohexyl)-N,N′-ethyleneurea,N-(2-hydroxyethyl)-N,N′-propyleneurea,N-(2-hydroxypropyl)-N,N′-propyleneurea,N-(3-hydroxypropyl)-N,N′-propyleneurea,N-(4-hydroxybutyl)-N,N′-propyleneurea,N-(6-hydroxyhexyl)-N,N′-propyleneurea,N-(3-hydroxy-2-ethylhexyl)-N,N′-propyleneurea,N-(3-hydroxy-2,4-diethyloctyl)-N,N′-propyleneurea,N-(2,2-di(hydroxymethyl)butyl)-N,N′-propyleneurea,N-(2,2-di(hydroxymethyl)propyl)-N,N′-propyleneurea,N-(2,2,2-tri(hydroxymethyl)ethyl)-N,N′-propyleneurea,N-(2-hydroxymethyl-2,2-dimethylethyl)-N,N′-propyleneurea,N-(5-hydroxy-3-oxapentyl)-N,N′-propyleneurea,N-(8-hydroxy-3,6-dioxaoctyl)-N,N′-propyleneurea,N-(7-hydroxy-4-oxaheptyl)-N,N′-propyleneurea,N-(3-amino-3,5,5-trimethylcyclohexyl)-N,N′-propyleneurea,N-(3-hydroxy-3,5,5-trimethylcyclohexyl)-N,N′-propyleneurea,N-(2-(methylamino)ethyl)-N,N′-propyleneurea,N-(2-(methylamino)propyl)-N,N′-propyleneurea,N-(3-(methylamino)propyl)-N,N′-propyleneurea,N-(4-(methylamino)butyl)-N,N′-propyleneurea,N-(6-(methylamino)hexyl)-N,N′-propyleneurea,N-(3-methylamino-2-ethylhexyl)-N,N′-propyleneurea,N-(3-methylamino-2,4-diethyloctyl)-N,N′-propyleneurea,N-(2,2-di((methylamino)methyl)butyl)-N,N′-propyleneurea,N-(2,2-di((methylamino)methyl)propyl)-N,N′-propyleneurea,N-(2,2,2-tri((methylamino)methyl)ethyl)-N,N′-propyleneurea,N-(2-(methylamino)methyl-2,2-dimethylethyl)-N,N′-propyleneurea,N-(5-methylamino-3-oxapentyl)-N,N′-propyleneurea,N-(8-methylamino-3,6-dioxaoctyl)-N,N′-propyleneurea,N-(7-methylamino-4-oxaheptyl)-N,N′-propyleneurea,N-(2-(ethylamino)ethyl)-N,N′-propyleneurea,N-(2-(ethylamino)propyl)-N,N′-propyleneurea,N-(3-(ethylamino)propyl)-N,N′-propyleneurea,N-(4-(ethylamino)butyl)-N,N′-propyleneurea,N-(6-(ethylamino)hexyl)-N,N′-propyleneurea,N-(3-ethylamino-2-ethylhexyl)-N,N′-propyleneurea,N-(3-ethylamino-2,4-diethyloctyl)-N,N′-propyleneurea,N-(2,2-di((ethylamino)methyl)butyl)-N,N′-propyleneurea,N-(2,2-di((ethylamino)methyl)propyl)-N,N′-propyleneurea,N-(2,2,2-tri((ethylamino)methyl)ethyl)-N,N′-propyleneurea,N-(2-(ethylamino)methyl-2,2-dimethylethyl)-N,N′-propyleneurea,N-(5-ethylamino-3-oxapentyl)-N,N′-propyleneurea,N-(8-ethylamino-3,6-dioxaoctyl)-N,N′-propyleneurea,N-(7-ethylamino-4-oxaheptyl)-N,N′-propyleneurea,N-(2-(butylamino)ethyl)-N,N′-propyleneurea,N-(2-(butylamino)propyl)-N,N′-propyleneurea,N-(3-(butylamino)propyl)-N,N′-propyleneurea,N-(4-(butylamino)butyl)-N,N′-propyleneurea,N-(6-(butylamino)hexyl)-N,N′-propyleneurea,N-(3-butylamino-2-ethylhexyl)-N,N′-propyleneurea,N-(3-butylamino-2,4-diethyloctyl)-N,N′-propyleneurea,N-(2,2-di((butylamino)methyl)butyl)-N,N′-propyleneurea,N-(2,2-di((butylamino)methyl)propyl)-N,N′-propyleneurea,N-(2,2,2-tri((butylamino)methyl)ethyl)-N,N′-propyleneurea,N-(2-(butylamino)methyl-2,2-dimethylethyl)-N,N′-propyleneurea,N-(5-butylamino-3-oxapentyl)-N,N′-propyleneurea,N-(8-butylamino-3,6-dioxaoctyl)-N,N′-propyleneurea,N-(7-butylamino-4-oxaheptyl)-N,N′-propyleneurea,N-(2-thioethyl)-N,N′-propyleneurea, N-(2-thiopropyl)-N,N′-propyleneurea,N-(3-thiopropyl)-N,N′-propyleneurea, N-(4-thiobutyl)-N,N′-propyleneureaor N-(6-thiohexyl)-N,N′-propyleneurea.

“Propyleneurea” may stand both for “1,2-propyleneurea” and for“1,3-propyleneurea”.

The compounds c) preferably comprise O-(2-hydroxyethyl) carbamate,O-(2-hydroxypropyl)carbamate, O-(3-hydroxypropyl) carbamate,O-(4-hydroxybutyl)carbamate, O-(6-hydroxyhexyl) carbamate,O-(2,2-di(hydroxymethyl)propyl)carbamate,O-(2-hydroxyethyl)N-methylcarbamate, O-(2-hydroxypropyl)N-methylcarbamate, O-(2-hydroxyethyl)N-ethylcarbamate,N-(2-hydroxyethyl)urea, N-(2-hydroxypropyl)urea,N-(3-hydroxypropyl)urea, N-(4-hydroxybutyl)urea, N-(6-hydroxyhexyl)urea,N-(2-hydroxyethyl)-N′-methylurea, N-(2-hydroxypropyl)-N′-methylurea,N-(3-hydroxypropyl)-N′-methylurea, N-(4-hydroxybutyl)-N′-methylurea orN-(6-hydroxyhexyl)-N′-methylurea, and with particular preferenceO-(2-hydroxyethyl)carbamate, O-(2-hydroxypropyl)carbamate orO-(4-hydroxybutyl)carbamate.

Suitable components d) include compounds having at least oneisocyanate-reactive group and at least one dispersing group.

Such compounds are represented for example by the formulaRG-R³-DGwhere

-   -   RG is at least one isocyanate-reactive group,    -   DG is at least one dispersing group, and    -   R³ is an aliphatic, cycloaliphatic or aromatic radical        containing from 1 to 20 carbon atoms.

Examples of RG are —OH, —SH, —NH₂ or —NHR⁴, in which R⁴ is as definedabove but may be different from the radical used there.

Examples of DG are —COOH, —SO₃H or —PO₃H and also their anionic forms,with which any desired counterion may be associated, e.g., Li⁺, Na⁺, K⁺,Cs⁺, Mg²⁺, Ca²⁺, Ba²⁺, ammonium, methylammonium, dimethylammonium,trimethylammonium, ethylammonium, diethylammonium, triethylammonium,tributylammonium, di-iso-propylethylammonium, benzyldimethylammonium,monoethanolammonium, diethanolammonium, triethanolammonium,hydroxyethyldimethylammonium, hydroxyethyldiethylammonium,monopropanolammonium, dipropanolammonium, tripropanolammonium,piperidinium, piperazinium, N,N′-dimethylpiperazinium, morpholinium orpyridinium.

R³ may be, for example, methylene, 1,2-ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, 1,3-butylene, 1,6-hexylene,1,8-octylene, 1,12-dodecylene, 1,2-phenylene, 1,3-phenylene,1,4-phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene,1,6-naphthylene, 1,2-cyclopentylene, 1,3-cyclopentylene,1,2-cyclohexylene, 1,3-cyclohexylene or 1,4-cyclohexylene.

Component d) preferably comprises, for example, mercaptoacetic acid,mercaptopropionic acid, thiolactic acid, mercaptosuccinic acid, glycine,iminodiacetic acid, sarcosine, alanine, β-alanine, leucine, isoleucine,aminobutyric acid, hydroxyacetic acid, hydroxypivalic acid, lactic acid,hydroxysuccinic acid, hydroxydecanoic acid, dimethylolpropionic acid,dimethylolbutyric acid, ethylenediaminetriacetic acid, hydroxydodecanoicacid, hydroxyhexadecanoic acid, 12-hydroxystearic acid,aminonaphthalenecarboxylic acid, hydroxyethanesulfonic acid,hydroxypropanesulfonic acid, mercaptoethanesulfonic acid,mercaptopropanesulfonic acid, aminomethanesulfonic acid, taurine,aminopropanesulfonic acid, and also their alkali metal, alkaline earthmetal or ammonium salts, and with particular preference comprises thespecified monohydroxycarboxylic and monohydroxysulfonic acids and alsomonoaminocarboxylic and monoaminosulfonic acids.

To prepare the dispersion, the abovementioned acids, where not alreadyin salt form, are fully or partly neutralized, preferably using alkalimetal salts or amines, preferably tertiary amines.

Suitable components e) include compounds containing at least twoisocyanate-reactive groups, examples being —OH, —SH, —NH₂ or —NHR⁵,where R⁵ has the same meaning as R⁴ above but may be different from R⁴.

These compounds are preferably diols or polyols, such as hydrocarbondiols having 2 to 20 carbon atoms, e.g., ethylene glycol,1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol,1,6-hexanediol, 1,10-decanediol,bis(4-hydroxycyclohexane)isopropylidene, tetramethylcyclobutanediol,1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol,pinanediol, decalindiol, etc., their esters with short-chaindicarboxylic acids, such as adipic acid, cyclohexanedicarboxylic acid,their carbonates, prepared by reacting the diols with phosgene or bytransesterification with dialkyl or diaryl carbonates, or aliphaticdiamines, such as methylene- and isopropylidenebis(cyclohexylamine),piperazine, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or1,4-cyclohexanebis(methylamine), etc., dithiols or polyfunctionalalcohols, secondary or primary amino alcohols, such as ethanolamine,diethanolamine, monopropanolamine, dipropanolamine etc., orthioalcohols, such as thioethylene glycol.

Also conceivable are diethylene glycol, triethylene glycol, dipropyleneglycol, tripropylene glycol, neopentyl glycol, pentaerythritol, 1,2- and1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol,2-ethyl-1,4-butanediol, 1,2-, 1,3- and 1,4-dimethylolcyclohexane,glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane,dipentaerythritol, ditrimethylolpropane, erythritol and sorbitol,2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol or2-(2-aminoethoxy)ethanol, bisphenol A, or butanetriol.

Also suitable, furthermore, are unsaturated polyetherols or polyesterolsor polyacrylate polyols having an average OH functionality of from 2 to10, and also polyamines, such as polyethyleneimine or polymers of, forexample, poly-N-vinylformamide containing free amine groups.

Particularly suitable here are the cycloaliphatic diols, such asbis(4-hydroxycyclohexane)isopropylidene, tetramethylcyclobutanediol,1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol or norbornanediol,for example.

Suitable components f) include compounds containing at least oneisocyanate-reactive group. These compounds may, for example, bemonoalcohols, mercaptans or monoamines containing 1 to 20 carbon atoms,e.g., methanol, ethanol, iso-propanol, n-propanol, n-butanol,iso-butanol, sec-butanol, tert-butanol, ethylene glycol monomethylether, ethylene glycol monoethyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, 1,3-propanediol monomethylether, 1,2-propanediol monoethyl ether, 1,2-propanediol monomethylether, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol,2-ethylhexanol, cyclopentanol, cyclohexanol, cyclooctanol,cyclododecanol, triethylene glycol monomethyl ether, triethylene glycolmonoethyl ether, n-pentanol, stearyl alcohol, cetyl alcohol, laurylalcohol, cyclopent-2-en-1-ol, cyclopent-3-en-1-ol, cyclohex-2-en-1-ol,allyl alcohol, methylamine, ethylamine, iso-propylamine, n-propylamine,n-butylamine, iso-butylamine, sec-butylamine, tert-butylamine,n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine,n-dodecylamine, 2-ethylhexylamine, stearylamine, cetylamine,laurylamine, dimethylamine, diethylamine, di-n-propylamine,di-iso-propylamine, di-n-butylamine, dihexylamine, dioctylamine,ethylmethylamine, iso-propylmethylamine, n-butylmethylamine,tert-butylmethylamine, iso-propylethylamine, n-butylethylamine,tert-butylethylamine, cyclopentylamine, cyclohexylamine,cyclooctylamine, cyclododecylamine, morpholine, piperidine, pyrrolidine,N-methylpiperazine, monoethanolamine, diethanolamine, monopropanolamine,dipropanolamine, methanethiol, ethanethiol, iso-propanethiol,n-propanethiol, n-butanethiol, iso-butanethiol, sec-butanethiol ortert-butanethiol.

Suitable components (B) include those compounds which are able tocrosslink with carbamates. Reactive groups of this kind include activemethylol or alkylalkoxy groups, especially methylalkoxy groups, on aminoresin crosslinkers, such as etherified reaction products of formaldehydewith amines, such as melamine, urea etc., phenol/formaldehyde adducts,siloxane or silane groups, and anhydrides, as are described, forexample, in U.S. Pat. No. 5,770,650.

Among the industrially widespread and widely known, preferred aminoresins it is possible with particular preference to use urea resins andmelamine resins, such as urea-formaldehyde resins, melamine-formaldehyderesins, melamine-phenol-formaldehyde resins or melamin-urea-formaldehyderesins, for example.

Suitable urea resins are those obtainable by reacting ureas withaldehydes, and which may if desired be modified.

Suitable ureas include urea, N-substituted ureas or N,N′-disubstitutedureas, such as N-methylurea, N-phenylurea, N,N′-dimethylurea,hexamethylenediurea, N,N′-diphenylurea, 1,2-ethylenediurea,1,3-propylenediurea, diethylenetriurea, dipropylenetriurea,2-hydroxypropylenediurea, 2-imidazolidinone (ethyleneurea),2-oxohexahydropyrimidine(propyleneurea) or2-oxo-5-hydroxyhexahydropyrimidine(5-hydroxypropyleneurea).

Particularly suitable aldehydes include formaldehyde, acetaldehyde,iso-butyraldehyde, and glyoxal.

Urea resins may if desired by partly or fully modified, modificationtaking place, for example, by reaction with monofunctional orpolyfunctional alcohols, ammonia and/or amines (cationically modifiedurea resins) or with (hydrogen) sulfites (anionically modified urearesins); in accordance with the invention, the alcohol-modified urearesins are particularly suitable.

Suitable modifying alcohols include C₁-C₆ alcohols, preferably C₁-C₄,and especially methanol, ethanol, iso-propanol, n-propanol, n-butanol,iso-butanol, and sec-butanol.

Suitable melamine resins are those obtainable by reacting melamine withaldehydes, and they may if desired by partly or fully modified.

Melamine-formaldehyde resins are products of the reaction of melaminewith aldehydes, examples being the aldehydes mentioned above, especiallyformaldehyde. If desired, the methylol groups obtained may be modifiedby etherification with the abovementioned monohydric or polyhydricalcohols. Additionally, the melamine-formaldehyde resins may also bemodified as described above by reaction with amines, aminocarboxylicacids or sulfites.

The action of formaldehyde on mixtures of melamine and urea or onmixtures of melamine and phenol produces melamine-urea-formaldehyderesins or, respectively, melamin-phenol-formaldehyde resins which maylikewise be used in accordance with the invention.

The abovementioned amino resins are prepared by conventional techniques.

Examples mentioned particularly are melamin-formaldehyde resins,including monomeric or polymeric melamine resins and fully or partlyalkylated melamine resins, urea resins, e.g., methylolureas such asformaldehyde-urea resins, alkoxyureas such as butylatedformaldehyde-urea resins, and also N-methylolacrylamide emulsions,iso-butoxymethylacrylamide emulsions, polyanhydrides, such aspolysuccinic anhydride, and siloxanes or silanes, e.g.,dimethyldimethoxysilanes.

Particular preference is given to amino resins such asmelamin-formaldehyde resins or formaldehyde-urea resins.

Likewise preferred are amino resins in which one or more amino groupshave been substituted by carbamate groups, as described in U.S. Pat. No.5,300,328.

As photoinitiators (C) it is possible to use photoinitiators known tothe skilled worker, examples being those referred to in “Advances inPolymer Science”, Volume 14, Springer Berlin 1974 or in K. K. Dietliker,Chemistry and Technology of UV and EB Formulation for Coatings, Inks andPaints, Volume 3; Photoinitiators for Free Radical and CationicPolymerization, P. K. T. Oldring (Ed.), SITA Technology Ltd, London.

Suitable examples include mono- or bisacylphosphine oxides, as describedfor example in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 orEP-A 615 980, examples being 2,4,6-trimethylbenzoyldiphenylphosphineoxide (Lucirin® TPO), ethyl 2,4,6-trimethylbenzoylphenylphosphinate,benzophenones, hydroxyacetophenones, phenylglyoxylic acid and itsderivatives, or mixtures of these photoinitiators. Examples that may bementioned include benzophenone, acetophenone, acetonaphthoquinone,methyl ethyl ketone, valerophenone, hexanophenone,α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone,4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene,4-aminobenzophenone, 4′-methoxyacetophenone, β-methylanthraquinone,tert-butylanthraquinone, anthraquinonecarbonylic esters, benzaldehyde,α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene,10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone,1-indanone, 1,3,4-triacetylbenzene, thioxanthen-9-one, xanthen-9-one,benzoin iso-butyl ether, chloroxanthenone, benzoin tetrahydropyranylether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether,benzoin iso-propyl ether, 7H-benzoin methyl ether,benzo[de]anthracen-7-one, 1-naphthaldehyde,4,4′-bis(dimethylamino)benzophenone, 4-phenylbenzophenone,4-chlorobenzophenone, Michler's ketone, 1-acetonaphthone,2-acetonaphthone, 1-benzoylcyclohexan-1-ol,2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone,o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine,benzo[a]anthracene-7,12-dione, 2,2-diethoxyacetophenone,2,2-dimethoxy-2-phenylacetophenone, benzil ketals, such as benzildimethyl ketal,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and2,3-butanedione.

Particularly suitable are nonyellowing or low-yellowing photoinitiatorsof the phenylglyoxalic ester type, as described in DE-A 198 26 712, DE-A199 13 353 or WO 98/33761.

Examples of further typical coatings additives (D) which may be usedinclude antioxidants, stabilizers, activators (accelerators), fillers,pigments, dyes, antistats, flame retardants, thickeners, thixotropicagents, surface-active agents, viscosity modifiers, plasticizers orchelating agents.

As accelerators for the thermal aftercure it is possible, for example,to use tin octoate, zinc octoate, dibutyltin dilaurate ordiaza[2.2.2]bicyclooctane.

It is also possible to add one or more initiators which can be activatedphotochemically and/or thermally, examples being potassiumperoxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide,di-tert-butyl peroxide, azobis-iso-butyronitrile,cyclohexylsulfonylacetyl peroxide, di-iso-propyl percarbonate,tert-butyl peroctoate or benzpinacol, and also, for example, thoseinitiators which can be activated thermally and have a half-life at 80°C. of more than 100 hours, such as di-t-butyl peroxide, cumenehydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylatedpinacols, which are available commercially, for example, under the tradename ADDID 600 from Wacker, or hydroxyl-containing amine N-oxides, suchas 2,2,6,6-tetramethylpiperidine-N-oxyl,4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, etc.

Other examples of suitable initiators are described in “PolymerHandbook”, 2nd ed., Wiley & Sons, New York.

Suitable thickeners include not only free-radically (co)polymerized(co)polymers but also customary organic and inorganic thickeners such ashydroxymethylcellulose or bentonite.

Chelating agents which can be used include, for example,ethylenediamineacetic acid and its salts and also β-diketones.

Suitable fillers include silicates, examples being silicates obtainableby hydrolyzing silicon tetrachloride, such as Aerosil® from Degussa,siliceous earth, talc, aluminum silicates, magnesium silicates, calciumcarbonates etc.

Suitable stabilizers embrace typical UV absorbers such as oxanilides,triazines, and benzotriazole (the latter obtainable as Tinuvin® gradesfrom Ciba-Spezialitätenchemie) and benzophenones. These may be usedalone or together with suitable free-radical scavengers, examples beingsterically hindered amines such as 2,2,6,6-tetramethylpiperidine,2,6-di-tert-butylpiperidine or derivatives thereof, e.g.,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate. Stabilizers are commonlyused in amounts of from 0.1 to 5.0% by weight, based on the solidcomponents present in the formulation.

The polyurethanes (A) of the invention are obtained by reactingcomponents a), b), and c) with one another.

The molar composition a):b):c) per 3 mol of reactive isocyanate groupsin a) is generally as follows:

-   -   b) 0.1-2.9, preferably 0.5-2.8, with particular preference        1.0-2.5, and in particular 1.5-2.5 mol of isocyanate-reactive        groups, and    -   c) 2.9-0.1, preferably 0.2-2.5, with particular preference        0.5-2.0 and in particular 0.5-1.5 mol of isocyanate-reactive        groups.

Following reaction of components a), b) and c) the polyurethane (A) maystill contain free isocyanate groups; preferably, however, more than 70%of the isocyanate groups present in a) before reaction have beenconsumed by reaction, with particular preference more than 80%, withvery particular preference more than 90%, and in particular more than95%.

For use of the polyurethanes in aqueous systems, it is preferred forsubstantially all of the isocyanate groups present to have been consumedby reaction.

The composition of the polyurethane dispersions of the invention is asfollows (per mole of reactive isocyanate group in the polyurethane (A))

-   -   d) 1-30 mol %, preferably 2-20 mol %, with particular preference        3-15 mol %, and in particular 5-10 mol % of isocyanate-reactive        groups,    -   e) 0-50 mol %, preferably 5-40 mol %, with particular preference        10-30 mol %, and in particular 15-25 mol % of        isocyanate-reactive groups,    -   f) 0-50 mol %, preferably 5-40 mol %, with particular preference        10-30 mol %, and in particular 15-25 mol % of        isocyanate-reactive groups,    -   (B) per mole of carbamate or urea end group present in the        polyurethane (A), 1-5 mol of compound (B), with particular        preference 1-3 mol, with very particular preference 1.1-2.5 mol,        and in particular 1.5-2 mol of groups which are reactive toward        carbamate or urea end groups,    -   (C) based on the overall weight, the finished polyurethane        dispersion may contain 0-10% by weight of (C), preferably 1-8%        by weight, with particular preference 2-7% by weight, and in        particular 3-5% by weight, and also    -   (D) based on the overall weight, the finished dispersion may        contain 0-50% by weight of components (D), preferably 5-40% by        weight, with particular preference 10-30% by weight, and in        particular 15-25% by weight.

The adduct formed from isocyanato-containing compound and the compoundcontaining groups that are reactive toward isocyanate groups isgenerally formed by mixing the components in arbitrary order, atelevated temperature if desired.

It is preferred to add the compound which contains groups that arereactive toward isocyanate groups to the isocyanato-containing compound,preferably in two or more steps.

With particular preference, the isocyanato-containing compound isintroduced initially and the compounds containing groups that arereactive toward isocyanate are added. In particular, theisocyanato-containing compound a) is introduced initially and then b)and, subsequently, c) are added. Thereafter, it is possible, if desired,to add further desired components.

In general, the reaction is conducted at temperatures between 5 and 100°C., preferably between 20 and 90° C., with particular preference between40 and 80° C. and in particular between 60 and 80° C.

For this reaction it is preferred to operate under anhydrous conditions.

Anhydrous means here that the water content of the reaction system isnot more than 5% by weight, preferably not more than 3% by weight, andwith particular preference not more than 1% by weight.

The reaction is preferably conducted in the presence of least onesuitable inert gas, e.g., nitrogen, argon, helium, carbon dioxide or thelike.

The reaction may also be conducted in the presence of an inert solvent,e.g., acetone, iso-butyl methyl ketone, toluene, xylene, butyl acetateor ethoxyethyl acetate. Preferably, however, the reaction is conductedin the absence of a solvent.

The polyurethanes of the invention are particularly suitable as binders,e.g., in coating materials, paints or varnishes.

The polyurethanes and polyurethane dispersions of the invention may beused with preference as coating materials. For this purpose they areadmixed where necessary with components (B) and also, where appropriate(C) and, where appropriate, (D).

The substrates are coated by conventional techniques that are known tothe skilled worker, involving the application of at least one dispersionor coating formulation of the invention to the target substrate in thedesired thickness and the removal of the volatile constituents of thedispersions, where appropriate with heating. If desired, this operationmay be repeated one or more times. Application to the substrate may takeplace in conventional manner, e.g., by spraying, troweling, knifecoating, brushing, rolling, roller coating, or flow coating. The coatingthickness is generally situated within a range from about 3 to 1 000g/m² and preferably from 10 to 200 g/m².

Also disclosed is a method of coating substrates, which involves adding,where appropriate, further typical coating additives and thermallycurable resins to the polyurethane of the invention, the polyurethanedispersions of the invention, or coating formulations, applying them tothe substrate and, if desired, drying them, curing them with electronbeams or UV exposure under an oxygen-containing atmosphere or,preferably under inert gas, where appropriate at temperatures up to thelevel of the drying temperature, and then subjecting them to thermaltreatment at temperatures up to 160° C., preferably between 60 and 160°C.

The method of coating substrates may also be implemented by firstapplying the polyurethanes or polyurethane dispersions or coatingformulations of the invention and then subjecting them to thermaltreatment at temperatures up to 160° C., preferably between 60 and 160°C., and then curing them with electron beams or by UV exposure underoxygen or, preferably, under inert gas.

If desired, the films that are formed on the substrate may be cured bymeans of heat alone. In general, however, the coatings are cured both byexposure to high-energy radiation and thermally.

If two or more films of the coating material are applied one above theother, it is possible if desired for a thermal and/or radiation cure totake place following each coating operation.

Examples of suitable radiation sources for the radiation cure includelow, medium and high pressure mercury lamps and also fluorescent tubes,pulsed emitters, metal halide lamps, electronic flash devices, by meansof which radiation curing without a photoinitiator is possible, orexcimer lamps. Radiation curing is effected by exposure to high-energyradiation, i.e., UV radiation or daylight, preferably light in thewavelength range from λ=200 to 700 nm, with particular preference fromλ=200 to 500 nm, and with very particular preference from λ=250 to 400nm, or by irradiation with high-energy electrons (electron beams; 150 to300 kev). Examples of radiation sources used include high pressuremercury vapor lamps, lasers, pulsed lamps (flashlight), halogen lamps orexcimer lamps. The radiation dose normally used for crosslinking in theUV cure is in the range from 80 to 3 000 mJ/cm².

It is of course also possible to use two or more radidation sources forthe cure, e.g., from two to four.

It is also possible for these sources each to emit in differentwavelength ranges.

If desired, irradiation may also be conducted in the absence of oxygen,e.g., under an inert gas atmosphere. Suitable inert gases preferablyinclude nitrogen, noble gases, carbon dioxide, or combustion gases.Irradiation may further take place by the coating material being coveredwith transparent media. Examples of transparent media include polymerfilms, glass or liquids, e.g., water. Particular preference is given toirradiation in the manner described in DE-A 199 57 900.

The invention additionally provides a method of coating substrates whichinvolves

-   -   i) coating a substrate with a dispersion, as described above,    -   ii) removing volatile constituents of the dispersion to form a        film, under conditions in which the initiator (C) does not yet        substantially form any free radicals,    -   iii) if desired, exposing the film formed in step ii) to        high-energy radiation, the film undergoing initial curing, and        then, if desired, mechanically working the article coated with        the precured film or contacting the surface of the precured film        with another substrate,    -   iv) finally curing the film thermally.

Steps iv) and iii) may also be carried out in the opposite order; inother words, the film may be cured first thermally and then withhigh-energy radiation.

The dispersions and coating formulations of the invention areparticularly suitable for the coating of substrates such as wood, paper,textile, leather, nonwoven, plastics surfaces, glass, ceramic, mineralbuilding materials, such as cement slabs and fiber cement panels, ormetals or coated metals, preferably of plastics or metals.

With particular preference the dispersions of the invention are suitableas or in exterior coatings, i.e., applications involving exposure todaylight; preferably of buildings or parts of buildings, interiorcoatings, traffic markings, coatings on vehicles and aircraft. Inparticular, the dispersions of the invention are used as or inautomotive clearcoat and topcoat materials.

The storage stability of the compositions of the invention is greaterthan that of their prior art counterparts on account of the fact thatthe compositions of the invention substantially contain only urea endgroups and carbamate end groups bonded via the oxygen atom, but do notcontain the highly reactive end groups which are otherwise the norm.

The only products which arise in the course of a cure are low-boiling,i.e., volatile, alcohols or amines, examples being the residues R₁—NH₂or R²—NH₂ in c) or the alcohols used as ethers in a melamine or urearesin.

The examples which follow are intended to illustrate the properties ofthe invention without, however, restricting it.

EXAMPLES

In this document all parts are to be understood as meaning parts byweight unless specified otherwise.

The pendulum hardness is determined in accordance with DIN 53157 on aglass plate substrate. It is a measure of the hardness of a coating.High pendulum hardness values represent a high coating hardness.

Example 1

Preparation of the Polyisocyanato Acrylate:

Hexamethylene diisocyanate (HDI) was introduced under nitrogenblanketing and 50 mol % (relative to isocyanate) of stabilizedhydroxyethyl acrylate was added. The mixture was heated to 80° C. and200 ppm by weight (based on the diisocyanate) of the catalystN,N,N-trimethyl-N-(2-hydroxypropyl)ammonium 2-ethylhexanoate were added.The temperature rose slowly to 120° C. Reaction was allowed to takeplace at this temperature and was stopped when the mixture had an NCOcontent of 16.8% by weight by adding 250 ppm by weight (based on thediisocyanate) of di-2-ethylhexyl phosphate. The reaction mixture wassubsequently freed from unreacted HDI in a thin-film evaporator at 135°C. and 2.5 mbar.

The NCO content following distillation was 11.8% by weight, theviscosity at 23° C. was 1 640 mPas.

Further Processing:

200 parts of this polyisocyanato acrylate containing urethane andallophanate groups are reacted with 68 parts of hydroxypropyl carbamate(Carbalink® HPC, Huntsman Corp.) in the presence of 0.05 part ofdibutyltin dilaurate, 0.13 part of hydroquinone monomethyl ether and0.27 part of 2,6-di-tert-butyl-p-cresol. The temperature rises to 85° C.The mixture is then stirred at 75° C. for 5 hours. The product is highlyviscous. The original NCO content of 11.8% has fallen to 0.1%.

Example 2

Preparation of a Dual-cure Polyurethane Acrylate Dispersion:

200 parts of the polyisocyanato acrylate from example 1, containingurethane and allophanate groups and having an NCO content of 11.8%, arereacted in a stirred tank with 20.6 parts of2,2-bis(4-hydroxycyclohexyl)propane and 20.4 parts of hydroxypropylcarbamate (Carbalink® HPC, Huntsman Corp.) in the presence of 0.25 partof 2,6-di-t-butyl-p-cresol, 0.12 part of hydroquinone monomethyl etherand 0.5 part of dibutyltin dilaurate, the temperature rising to 85° C.,and then stirred at 60° C. for 5 hours. The NCO value is 1.7%.

Then 3.8 parts of thioglycolic acid and 6.7 parts of hydroxyethylacrylate are added and stirring is continued at 65° C. for 4 hours. Theresidual NCO value is 0.18%. The product is neutralized with 4.6 partsof triethylamine, 1.5 parts of methanol are added, and the mixture isstirred at room temperature for 1.5 hours. It is then dispersed inwater.

Example 3

Dual Cure Coating Material

To 20 parts of binder from example 1) there are added 3.7 parts ofLuwipal® 066, a commercially available methanol-etherified melamineresin from BASF AG, 2 parts of a photoinitiator mixture of 3.5 partsIrgacure® 184 (Ciba) and 0.5 part Lucirin® TPO (BASF).

Production of Films

The coating material is applied to different substrates in filmthicknesses of approximately 40 μm and is treated as follows: it isirradiated using 2 UV lamps (each 80 W/cm) on a conveyor belt at thestated speed and then heated in a gradient oven for the times and at thetemperatures indicated.

The applied coating film is liquid and tacky (pendulum hardness <5 s).Following exposure at 2*5 m/min under the IST exposure unit and 5 minheating at 120° C., the pendulum hardness increases to 110 s, and after30 min heating it increases to 130 s.

Example 4

Dual Cure Coating Material from a Dispersion

To 50 parts of dispersion from example 2) there are added 5 parts ofLuwipal® 066, a commercially available methanol-etherified melamineresin from BASF AG, 2 parts of a photoinitiator mixture of 3.5 partsIrgacure® 184 (Ciba) and 0.5 part Lucirin® TPO (BASF).

Production of Films

The dispersion is applied to different substrates in film thicknesses ofapproximately 40 μm and is treated as follows: it is irradiated using 2UV lamps (each 80 W/cm) on a conveyor belt at the stated speed and thenheated in a gradient oven for the times and at the temperaturesindicated.

The applied coating film is liquid and tacky (pendulum hardness <5 s).Following exposure at 2*5 m/min under the IST exposure unit and 5 minheating at 120° C., the pendulum hardness increases to 125 s, and after30 min heating it increases to 142 s.

1. A polyurethane (A), comprising as constituent components: a) at least one organic aliphatic or cycloaliphatic allophanate group containing polyisocyanate, b) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group andlor a cationically polymerizable group, c) at least one compound having at least one isocyanate-reactive group and a carbamate or urea end group, d) optionally, at least one compound containing at least one isocyanate-reactive group and at least one dispersing group, e) optionally, at least one compound containing at least two isocyanate-reactive groups, and f) optionally, compounds other than a) to d) containing at least one isocyanate-reactive group.
 2. The polyurethane as claimed in claim 1, further comprising: (B) at least one compound containing at least one group that can crosslink with the carbamate groups.
 3. A polyurethane dispersion, comprising; (A) a polyurethane as claimed in claim 1, wherein component d) is present, (B) at least one compound containing at least one group that can crosslink with the carbamate groups, (C) optionally; one or more initiators which can be activated photochemically and/or thermally, and (D) optionally, further typical coatings additives.
 4. A coating material comprising a polyurethane dispersion as claimed in claim
 3. 5. A polyurethane as claimed in claim 2, wherein component (B) comprises at least one amino resin.
 6. A method of coating substrates, which comprises: radiation-curing a substrate coated with a material comprising the polyurethane as claimed in claim 1 and heat-treating the coated substrate at temperatures up to 160° C.
 7. The method as claimed in claim 6, wherein the heat treatment takes place at a temperature ranging from 60 to 160° C.
 8. The method as claimed in claim 6, wherein the radiation curing is carried out under inert gas.
 9. A binder comprising the polyurethane as claimed in claim
 1. 10. A material for coating metals or plastics comprising the polyurethane as claimed in claim
 1. 11. An automotive paint or automotive topcoat comprising the polyurethane as claimed in claim
 1. 12. A coating material comprising: a polyurethane (A) as claimed in claim 1, (B) at least one compound having at least one group that can crosslink with the carbamate groups, (C) optionally, one or more initiators which can be activated photochemically and/or thermally, and (D) optionally, further typical coatings additives.
 13. The polyurethane as claimed in claim 1, wherein said at least one organic aliphatic or cycloaliphatic allophanate group containing polyisocyanate is prepared by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with a polyhydric alcohol selected from the group consisting of trimethylolpropane, neopentyl glycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, ethylene glycol, diethylene glycol, glycerol, 1,2-dihydroxypropane and mixtures thereof such that the allophonate has an NCO content ranging from 12 to 20% by weight and an average NCO functionality of 2.5 to
 3. 14. The polyurethane as claimed in claim 1, wherein, per 100 g of compound (b), the compound contains at least 0.01 mol of unsaturated free-radically or cationically polymerizable groups, and, per 100 g of compound (c), the compound contains at least 0.01 mol of carbamate or urea end groups.
 15. The polyurethane as claimed in claim 1, wherein compound (d) has the formula: RG-R³-DG, wherein RG is at least one isocyanate-reactive group selected from the group consisting of —OH, —SH, —NH₂ and —NHR⁴, wherein R⁴ is hydrogen or an alkyl group containing 1 to 4 carbon atoms; DG is at least one dispersing group selected from the group consisting of —COOH, —SO₃H, —PO³H and the anionic forms of these groups; and R³ is an aliphatic, cycloaliphatic or aromatic radical containing from 1 to 20 carbon atoms.
 16. The polyurethane as claimed in claim 1, wherein compound (b) is a carbamate compound of the formula: R—O—(CO)—NH—R¹ or a urea compound of the formula: R—(NR¹)—(CO)—NN—R², wherein R is an aliphatic, cycloaliphatic or aromatic radical of 2 to 20 carbon atoms containing at least one isocyanate-reactive group selected from the group consisting of —OH, —SH, —NH₂ and —NHR⁴, wherein R⁴ is hydrogen or an alkyl group containing 1 to 4 carbon atoms; and R¹, R² and R⁴ independently of each other are hydrogen or an alkyl group containing 1 to 4 carbon atoms.
 17. The polyurethane as claimed in claim 1, wherein components a):b):c) are present in a molar ratio amount, per three mole amount of reactive isocyanate group in (a) is: b) 0.1 to 2.9, and c) 2.9to 0.1.
 18. The polyurethane as claimed in claim 17, wherein components a):b):c) are present in a molar ratio amount, per three mole amount of reactive isocyanate group in (a) is: b) 0.5 to 2.8, and c) 0.2 to 2.5. 